US9863044B2 - Method for electroless metallization - Google Patents

Method for electroless metallization Download PDF

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US9863044B2
US9863044B2 US14/042,527 US201314042527A US9863044B2 US 9863044 B2 US9863044 B2 US 9863044B2 US 201314042527 A US201314042527 A US 201314042527A US 9863044 B2 US9863044 B2 US 9863044B2
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group
solution
film
electroless
free radical
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Maria Anna Rzeznik
Philip D. Knudsen
Xuesong Wang
Martin W. Bayes
Yuhsin Tsai
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Rohm and Haas Electronic Materials LLC
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
    • C09D179/02—Polyamines
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1646—Characteristics of the product obtained
    • C23C18/165—Multilayered product
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
    • C23C18/1872—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment
    • C23C18/1886—Multistep pretreatment
    • C23C18/1893—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1646—Characteristics of the product obtained
    • C23C18/165—Multilayered product
    • C23C18/1651—Two or more layers only obtained by electroless plating
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1646—Characteristics of the product obtained
    • C23C18/165—Multilayered product
    • C23C18/1653—Two or more layers with at least one layer obtained by electroless plating and one layer obtained by electroplating
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/38—Coating with copper
    • C23C18/40—Coating with copper using reducing agents

Definitions

  • the presently disclosed embodiments relate generally to a method for forming a polymerized film on a surface of a non-conductive material and subsequently forming a metallic film on the surface without the aid of a traditional conditioner. More particularly, the embodiments relate to a method for forming an electrolessly plated metal film with strong adhesion on a smooth surface of non-conductive material without the aid of a traditional conditioner, using the polymerized film.
  • Electroless metallization is a method for obtaining a thin metallic film on materials such as metals, ceramics or plastics by a series of process steps, including the use of a conditioner, microetch, catalyst (activation) and electroless plating bath.
  • the mostly popular catalysts for electroless plating during the past 30 years are Pd/Sn colloids in which palladium colloidal particles are stabilized by tin chloride.
  • the surface charge of a dielectric substrate Prior to electroless plating, the surface charge of a dielectric substrate is typically negative. Due to electrostatic repulsion, the negative charge on the substrate will typically inhibit the adsorption of catalyst which is a negative charged colloid. The initiation of electroless metallization can be difficult if there is insufficient catalyst adsorption.
  • a traditional conditioner step is often used.
  • Typical constituents of a traditional conditioner include cationic surfactants, which provide positively-charged groups to change the substrate from negatively to partially positively charged, so that the adsorption of the catalyst can be improved.
  • the interaction between the substrate and the catalyst is enhanced by a traditional conditioner via electrostatic attraction.
  • the reliability of circuits relies heavily on the adhesion between the deposited metal layer and the dielectric substrate. Poor adhesion may lead to unacceptable failures, such as “peel-off” or blistering.
  • the electrostatic attraction from the traditional conditioner may not be strong enough to build up sufficient adhesion between the deposited metal layer and the dielectric substrate.
  • Roughening the surface of dielectric substrates for example by using a de-smear process, is often performed before electroless plating to increase the metal adhesion. Sufficient adhesion between the deposited metal layer and the dielectric substrates is then provided by the roughness of the dielectric substrate. Good adhesion is more difficult to obtain on a smooth surface using such process flows.
  • a conditioner In order to meet the requirements of the electronics industry for fine line circuits, a conditioner needs to be capable of providing high adhesion to a smooth (low profile) surface, as well as modifying the surface charge of dielectric substrates to improve the adsorption of a negatively charged catalyst.
  • Marine mussel organisms are known for their ability to bind strongly to such varied surfaces as rocks, pilings, and ship hulls.
  • the adhesive characteristics of mussel adhesive proteins are believed to be due to the presence of 3,4-dihydroxyphenylalamine (DOPA).
  • DOPA 3,4-dihydroxyphenylalamine
  • P. B. Messersmith et al. SCIENCE, 2007, Vol 318, page 426-430 discloses the use of dopamine to mimic the ability of mussel's adhesive protein to adhere to a surface of materials.
  • a thin, surface-adherent polydopamine film can be formed onto a wide range of inorganic and organic substrates through simple dip-coating of these substrates in an aqueous solution of dopamine at room temperature for 24 hours.
  • Electroless silver or copper deposition was performed on the polydopamine coated surfaces to form a layer of silver or copper.
  • CN10182678A discloses a polydopamine-assisted electroless silver process, in which dip coating of dopamine for 0 to 48 hours at room temperature was used.
  • US2010/0021748A discloses a process comprising the steps of treating a substrate with a catecholamine solution including dopamine, to form a polycatecholamine layer followed by electroless plating.
  • the dopamine self-polymerization process typically requires room temperature treatment for about 24 hours. Coupled with the relatively high cost of dopamine, the long dwell time of dopamine treatment is a barrier to commercial application. In addition, the pH range that is suitable for the self-polymerization of dopamine is quite narrow (6.5-9.5). Outside this pH range, the self-polymerization rate of dopamine becomes extremely low.
  • the inventors of this invention have found a method to form a multi-functional polymer film on a smooth surface through simple dip-coating of a material in a solution comprising two specific chemicals.
  • the resulting film allows for electroless metallization, without the aid of a traditional conditioner, with enhanced adhesion between the deposited metal layer and the material. This is especially suitable for a dielectric substrate with a smooth surface.
  • Another aspect of this invention is a method to form a polymerized film described above, comprising the step of contacting the surface of the material with a free radical initiator solution prior to the step contacting the material with the solution comprising (A) and (B) above.
  • a further aspect of this invention is a method for forming an electrolessly plated film on a smooth surface of a non-conductive material with strong adhesion, without the aid of a traditional conditioner using the above polymerized film.
  • FIG. 1 is a series of standard images for back light rating assessment.
  • FIG. 2 is a photomicrograph of backlight test for Example 19.
  • FIG. 3 is a photomicrograph of backlight test for Example 21.
  • the method includes the step of contacting a surface of a material with a solution comprising (A) an amine compound having at least two functional groups, where at least one of the functional group is an amino group and (B) an aromatic compound having at least one hydroxyl group on the aromatic ring.
  • Amine compounds of this embodiment are those compounds having at least two functional groups, where at least one of the functional groups is an amino group.
  • the functional groups can be selected from any kind of functional group, even if the compound can react with (B) the aromatic compounds described in detail later. Examples of such functional groups include, but are not limited to, amino groups and phenolic hydroxyl groups. Preferably, the other functional groups are amino groups.
  • Amino groups include primary amino groups, secondary amino groups, and nitrogen containing heterocyclic groups.
  • Amine compounds can be aliphatic compounds or aromatic compounds. When chemical resistance of the polymerized film is required, an aromatic amine such as tyramine is preferably used. When flexibility is required, an alkyl diamine having longer carbon chain such as hexamethylene diamine (HMDA) is preferably used.
  • HMDA hexamethylene diamine
  • H 2 N—R 1 —NH 2 Formula 1a wherein R 1 is selected from the group consisting of C 1 to C 24 linear or branched alkylene and aromatic alkylene.
  • R 1 is selected from the group consisting of C 1 to C 24 linear or branched alkylene and aromatic alkylene.
  • H 2 N—R 1 —NH—R 2 —NH 2 Formula 2a wherein R 1 and R 2 are selected independently from the group consisting of C 1 to C 24 linear or branched alkylene and aromatic alkylene.
  • R 1 , R 2 , and R 3 are selected independently from the group consisting of C 1 to C 20 linear or branched alkylene and aromatic alkylene.
  • R 1 , R 2 , and R 3 are selected independently from the group consisting of C 1 to C 20 linear or branched alkylene and aromatic alkylene.
  • R 1 , R 2 , R 3 , R 4 , and R 5 are selected independently from the group consisting of C 1 to C 16 linear or branched alkylene and aromatic alkylene.
  • n is an integer from 1 to 1500.
  • R 6 is selected from the group consisting of
  • Amine compounds can be used as a mixture of two or more kinds of amine compounds.
  • the amount of (A) amine compounds in the solution is 2 mmol/L to 2000 mmol/L, preferably 10 mmol/L to 400 mmol/L.
  • Aromatic compounds of this embodiment have at least one hydroxyl group connected to an aromatic ring.
  • the aromatic compounds Preferably, the aromatic compounds have two hydroxyl groups; more preferably, they may have two hydroxyl groups at ortho or para position to each other.
  • Aromatic compounds can be phenyl, naphthyl, or any other aromatic compounds.
  • the preferable aromatic compound is a phenyl compound.
  • a hydroxyl group connected to an aromatic ring such as catechol is oxidized and the aromatic compound is converted to a quinone. Since the oxygen atom of quinone is an electron-withdrawing group, quinone has activated carbon atoms on the aromatic ring. Michael Addition may occur at the activated carbon atoms on the aromatic ring with the amino group of the amine compound, and the amine compound and the aromatic compound are combined.
  • the inventors have found that the copolymerization rate of diamine with resorcinol with two hydroxyl groups at meta-position or phenol with one hydroxyl group at room temperature is slower than that of catechol or hydroquinone with two hydroxyl groups at ortho-position and para-position, respectively. Therefore, it is believed that compounds with two hydroxyl groups at the ortho- or para-position may be easier to form ketone groups and undergo a Michael Addition reaction with amine compounds than that with two hydroxyl groups at meta-position.
  • R 8 is selected from the group consisting of H, CH 3 , OH, phenyl, CN, NO 2 , propanoic acid, ethylamine, formic acid and formaldehyde
  • R 9 and R 10 are independently selected from H and OH.
  • a mixture of aromatic compounds can be used.
  • the amount of (B) aromatic compounds in the solution is 2 mmol/L to 2000 mmol/L, preferably 10 mmol/L to 400 mmol/L.
  • the medium of the solution is preferably water.
  • RO water or de-ionized water can be used.
  • a mixture of water with organic solvents such as methanol, ethanol, propanol, ethylene glycol, propylene glycol, propylene glycol or tetrahydrofuran may also be used as the medium of this invention.
  • a film is formed on the surface of the material. It is believed that the film is a copolymerized film of (A) with (B) via Michael Addition between (A) and (B), as well as coupling between (B) and (B) or (B) and (A).
  • chemical bonds between the organic surfaces and the copolymer(A+B) film might be formed via free radical or Michael Addition reactions.
  • coordination bonds between the inorganic surfaces with the copolymer(A+B) film might be built up via coordination reaction.
  • the mole ratio of the functional groups within (A) to the functional groups within (B) in the solution may vary such as 10:1 to 1:10.
  • the preferable mole ratio depends on the required properties of the film and the functionality on (A) and (B).
  • Amino groups potentially possess positive charges, whereas hydroxyl groups on aromatic rings potentially possess negative charges.
  • the charge distribution of the polymerized film can be modified.
  • a negative charged catalyst such as a Pd/Sn colloid
  • a positively charged copolymer(A+B) film is preferred because of better adsorption of a negatively charged catalyst.
  • the polymerized film is used for an electroless plating process using a Pd/Sn colloid catalyst such as in the current industrial electroless plating techniques, and when (A) is a diamine compound and (B) is a di-hydroxyl phenyl compound such as catechol, the preferable mole ratio of (A) to (B) varies from 4:1 to 1:1, more preferably is 2:1.
  • a positively charged catalyst is developed and used, a negatively charged copolymer(A+B) film might be preferred.
  • the step of contacting a surface of a material with a solution comprising (A) and (B) is conducted via any kind of methods, such as dipping or spraying.
  • the temperature range for contacting a material with the solution is from 5 to 99 degree C.
  • the dwell time of contacting a material with the solution depends on the temperature of the solution.
  • the time for contacting a material with the solution is preferably 3 hours to 3 days, more preferably 0.5 day to 1 day.
  • the time is preferably 0.1 hour to 8 hours, more preferably 0.5 hour to 4 hours.
  • Another aspect of this invention is a method comprises the step of: contacting a surface of a material with a free radical initiator solution prior to contacting with the solution comprising (A) and (B).
  • a free radical initiator solution comprising (A) and (B).
  • catechol oxidizes enzymes, present in mussels-adhesive-protein secretions, convert the dihydroxyphenyl group of DOPA into highly reactive o-quinone functionalities.
  • Michael Addition of side-chain amino groups from lysine residues to DOPA-quinone residues can be expected.
  • free radical species might build covalent bonds between o-semiquinones to increase cohesion (cross-links) and enable coupling to organic materials to enhance interfacial adhesion (adhesive reaction).
  • the temperature of the solution comprising (A) and (B) is increased from 20° C. to 80° C., the oxidization rate of hydroxyphenyl group increases greatly.
  • (B) is catechol, the generation of o-quinine becomes rapid, while the concentration of free radical o-semiquinone (half oxidized dihydroxyphenyl) may fall.
  • free radicals are believed to play a key role in both adhesive (coupling) and cohesive (cross-link) reactions, lower levels of free radical may reduce improvements in adhesive strength.
  • a free radical initiator is introduced by contacting the material with an organic solution of free-radical initiator.
  • Preferable free radical initiators are organic-soluble free radical initiators with limited water-solubility, because such free radical initiators are compatible with the surface of the dielectric material and can remain on the surface after contacting with an aqueous solution comprising (A) and (B).
  • free radical initiators include, but are not limited to, 2,2′-Azobis(2-methylbutyronitrile), Dimethyl 2,2′-azobis(2-methylpropionate), AIBN (2,2-azobisisobutyronitrile), ADMVN (2,2′-Azobis(2,4-dimethyl)valeronitrile)), and 2,2′-Azobis(4-methoxy-2.4-dimethyl valeronitrile).
  • 2,2′-Azobis(2-methylbutyronitrile) Dimethyl 2,2′-azobis(2-methylpropionate)
  • AIBN 2,2-azobisisobutyronitrile
  • ADMVN 2,2′-Azobis(2,4-dimethyl)valeronit
  • Preferable medium of the solution is an organic solvent such as toluene, PGMEA (propylene glycol monomethyl ether acetate), IPA (isopropyl alcohol), ethyl acetate, acetone, or methanol, depending on the specific free radical initiator selected.
  • organic solvent such as toluene, PGMEA (propylene glycol monomethyl ether acetate), IPA (isopropyl alcohol), ethyl acetate, acetone, or methanol, depending on the specific free radical initiator selected.
  • the concentration of the free radical initiator solution is preferably 0.003 to 0.3 mol/L, more preferably 0.02 to 0.2 mol/L.
  • the temperature of contacting a material with the free radical initiator solution is, preferably ⁇ 10 to 40 degree C., more preferably, around room temperature.
  • the time of contacting a material with the free radical initiator solution is preferably 0.1 second to 0.5 hour, more preferably, 3 seconds to 3 minutes.
  • the conditions of the following step should match with the kind of free radical initiator so that the temperature and dwell time of contacting with the solution comprising (A) and (B) should be determined from the half-life of each initiator.
  • the temperature and dwell time of the following step matches at 80 degree C. for 2 to 4 hours, but if ADMVN is used, it should be carried out at 65 degree C. for 2 to 4 hours.
  • a further aspect of this invention is a method for forming a metallic film on a non-conductive surface of a material, which comprises the following steps;
  • a step for applying a catalyst solution may be conducted.
  • catalysts can be used for this step, such as Pd/Sn colloid or ionic catalysts containing Pd or Ag ions.
  • concentration, temperature and time conventional technologies could be applied.
  • CATAPOSITTM 44 Catalyst Pd/Sn colloidal catalyst
  • CATAPREPTM 404 Pre-dip protecting salt for Pd/Sn catalyst
  • a material is dipped in 270 g/L of CATAPREPTM 404 Pre-dip aqueous bath at 20 to 35 degree C.
  • the material is then dipped in an aqueous solution containing 15 to 30 mL/L CATAPOSITTM 44 Catalyst and 270 g/L of CATAPREPTM 404 Pre-dip at 32 to 52 degree C. for 4 to 5 minutes.
  • the necessity for a catalyst step depends on the electroless plating bath used for the metallization.
  • an electroless plating bath including chelating agent, reducing agent, acid/base/pH adjuster, a less strong chelating agent together with a stronger reducing agent may allow electroless plating without the use of a catalyst step. Therefore, if a plating process without a catalyzing step is adopted, (A) and (B) should be selected so that the polymerized film has high reductibility as mentioned above.
  • Step 2 is an electroless metal plating step on the surface of a material on which a polymerized film has been formed.
  • the surface of the material is electrolessly plated with one or more metallic layers, such as copper, using an electroless metal plating bath.
  • electroless metal plating baths may be used. Such baths are well known in the art.
  • Metals which may be deposited on the surface of the material include, but are not limited to, copper, nickel, gold, silver and copper/nickel alloys.
  • nickel or copper is deposited on the surface of the materials.
  • CIRCUPOSITTM 880 ELECTROLESS COPPER, CUPOSITTM 253 ELECTROLESS COPPER, CIRCUPOSITTM 3350 ELECTROLESS COPPER all commercially available from Dow Electronics Material can be used.
  • Conventional electroless processes may be applied. For example, when a copper electroless plating bath is used, a material is dipped in an electroless plating bath including 45 mL/L CIRCUPOSITTM 880 E, 10 mL/L CIRCUPOSITTM 880 A, 28 mL/L CUPOSITTM Z, 25 mL/L CIRCUPOSITTM 880 C, and 15 mL/L CUPOSITTM Y at 30 to 34 degree C. for 15 to 45 minutes.
  • the material may undergo further processing.
  • Further processing may include additional electroless or electrolytic metal plating on the material, for example, copper, gold, silver, tin and alloys thereof.
  • Conventional electrolytic metal bathes may be used. Such bathes are well known in the art.
  • the material is optionally rinsed with water.
  • the method of this invention provides good electroless metal coverage on treated surface and better adhesion between a non-conductive surface of a material and a deposited metallic film without the use of a traditional conditioner. While the mechanism of adhesion building up is not fully understood, it is believed that chemical bonds, such as coordination bonds or covalent bonds, may be formed during the treatment disclosed by this invention, which contribute to the better adhesion results.
  • the pH of dopamine solution is buffered with 0.010 mol/L tris(hydroxymethyl)aminomethane and HCl
  • the pH of aqueous solution of monomer pairs is either buffered with K 2 HPO 4 /Citric Acid in the pH range of 3.0 to 8.0, or with H 3 BO 3 /KCl/NaOH in the pH range of 8.0 to 10.0.
  • Examples 1 to 12 provide some monomer-pair examples that are capable of in-situ polymerization in an aqueous solution and are capable of forming a water insoluble copolymer(A+B) film on a dielectric substrate. These copolymer(A+B) films show conditioner functionality, which increase the electroless copper coverage on glass cloth coupons without the use of a traditional conditioner.
  • Glass cloth coupons were obtained from glass-fiber reinforced bare epoxy laminates S1141 (Size: 50 mm*150 mm*1 mm, Supplier: Shengyi Technology Co. Ltd., Glass transition temperature: 140 ⁇ 150 degree C., Abbreviated as bare laminates).
  • the bare laminate coupons were first immersed in 98% H 2 SO 4 for 1 day to dissolve the epoxy resin and expose the glass cloth, then water rinsed for 5 minutes to clean the surface of glass cloth. This treatment was then repeated at least once to minimize epoxy residues. After final rinsing, the glass cloth coupons were oven dried at 120° C. for 4 hours.
  • the dried glass cloth coupon was contacted with a free radical initiator solution.
  • the glass coupon was dipped in a free radical initiator solution comprising 0.2 mol/L of AIBN (Azobisisobutyronitrile) in toluene at room temperature for 1 minute, and then dried in a fume hood at room temperature for 5 minutes.
  • AIBN Azobisisobutyronitrile
  • the glass cloth coupon was contacted with a solution comprising (A) and (B).
  • a solution comprising 0.026 mol/L of hexamethylene diamine and 0.013 mol/L of catechol was prepared using a K 2 HPO 4 /Citric Acid buffer solution. The pH of the solution was 4.5.
  • the glass cloth coupon was then dipped in the above described aqueous solution at 80 degree C. for 4 hours. A water insoluble copolymer(A+B) film was formed on the surface of the treated glass cloth coupon.
  • the treated glass cloth coupon with the copolymer(A+B) film was treated in an electroless copper plating process without a traditional conditioner step.
  • the coupon was dipped in a Microetch bath at room temperature for 1 minute, which contained 50 g/L of PREPOSITTM Etch 748 (Dow Electronics Materials) and 20 mL/L 98% H 2 SO 4 (Sigma-Aldrich), and then rinsed with R.O. water for 3 minutes. After that, the coupon was dipped in 270 g/L of CATAPREPTM 404 PreDip (Dow Electronics Materials) at 23 degree C. for 1 minute. Next, the glass cloth coupon was dipped in a catalyst bath at 40 degree C.
  • Examples 2 to 8 were processed in the same way as Example 1, except that the monomer pairs ((A)+(B)) and the mole ratio between them within procedure (3) were changed as indicated in Table 2.
  • the basic concentration was 0.013 mol/L.
  • the initial concentration of that monomer in the treatment bath was obtained.
  • a water insoluble copolymer(A+B) film was formed on the surface of glass cloth coupon after the “(A)+(B) solution treatment”, and an electroless copper plated film was formed after electroless plating without a traditional conditioner step.
  • Examples 9 and10 were processed in the same way as Example 1, except that the chemicals, the mole ratio between them, treatment temperature and dwell time of treatment within procedure (3) were changed as indicated in Table 2 and step (2) was not conducted.
  • the basic concentration was 0.013 mol/L.
  • the initial concentration of that monomer in the treatment bath was obtained.
  • a water insoluble copolymer(A+B) film was formed on the surface of glass cloth coupon after the “(A)+(B) solution treatment”, and an electroless copper plated film was formed after electroless plating without a traditional conditioner step.
  • Example 11 is a blank control of Example 1 to 8. It was processed in the same way as Example 1, except that step (2) was conducted using toluene without the presence of any free radical initiator, and step (3) was conducted using distilled water alone, without any solute. Only a very small amount of electroless copper was deposited on the surface of the glass cloth coupon after electroless plating without a traditional conditioner step. No continuous film of electroless copper film was formed.
  • Example 12 is a blank control of Example 9 and 10. It was processed in the same way as Example 9 and 10, except that step (3) was conducted using distilled water alone, without any solute. Only a very small amount of electroless copper was deposited on the surface of the glass cloth coupon after electroless plating without a traditional conditioner step. No continuous film of electroless copper film was formed.
  • copolymer(A+B) films formed by examples 1 thru 9 monomer pairs ((A)+(B)), as well as the polydopamine film formed by dopamine at room temperature show conditioner functionality. They are capable of increasing copper coverage on glass cloth coupons without the use of a traditional conditioner.
  • Examples 13 to 17 There are two aims for Examples 13 to 17. One aim was to compare the conditioner functionality of monomer pair treatment with that of dopamine treatment at 80 degree C. for 2 to 4 hours, by the back light test. The other aim was to examine the benefit of free radical initiator treatment to the conditioner functionality of monomer pair treatment.
  • a quantitative measurement of electroless copper coverage was a back light test, which measures the degree of electroless copper coverage in plated through holes, which contain areas of resin, glass fiber tips, and transverse glass fibers.
  • the back light test was carried out on small sections cut from drilled laminates, containing a number of holes, aligned along the same axis.
  • the diameter of the holes chosen was 1 millimeter.
  • the holes to be evaluated were extracted with a diamond saw. The holes were cut as close as possible to their center axis, while ensuring the holes were free of burrs or other debris and that the thickness of the coupon (from back surface to the middle of the holes) was less than 3 mm to allow light transmission through the sample to allow light to penetrate for the back light test.
  • An optical microscope capable of 50 to 1500 magnifications was used to carry out the back light test. Each of the holes was individually assessed by comparing with a series of standard images shown in FIG. 1 .
  • Transmitted light was visible in any areas within the holes where there was incomplete electroless copper coverage.
  • a numerical scale of 0.0 ⁇ 5.0 was used as back light ratings, where 5.0 represents a completely copper coverage on both resin areas and glass fiber areas.
  • Back light ratings equal to or above 4.5 represent substantially complete copper coverage on resin and glass fiber areas. Only occasional glass tip voids were observed.
  • Back light ratings equal to or above 4.0 indicated that the majority of resin and glass fiber areas had copper coverage, but voids were found on some glass tip areas and sometimes on transverse glass fiber areas.
  • a back light rating ranging from 2 to 3.5 represented good copper coverage on resin areas, but poor copper coverage on glass areas (both glass tip and transverse glass fiber area).
  • a back light rating lower than 2 means minimal copper coverage was found either on resin areas or on glass fiber areas.
  • the back light ratings shown in this invention were the average of the values for 10 holes.
  • Example 2 Glass cloth coupons same as in Example 1 were used as samples for film formation test and electroless copper coverage tests, and copper clad laminate S1141 with 1 mm diameter drilled holes (Size: 35 mm*100 mm*2 mm, 20 holes per coupon, Shengyi Technology Co. Ltd., glass transition temperature: 140 to 150 degree C., abbreviated as drilled laminates) were used as samples for back light tests. Drill laminates were processed through the de-smear process shown below, which included a sweller, an oxidation, and a neutralizer bath treatment. Glass cloth coupons were not treated in the de-smear process.
  • the drill laminates were dipped in a sweller bath at 75 degree C. for 5 minutes, which contained 125 mL/L CIRCUPOSITTM MLB Conditioner 211 (Dow Electronics Materials) and 115 mL/L CUPOSITTM Z (Dow Electronics Materials), and then rinsed with R.O. water for 3 minutes.
  • the drilled laminates were then dipped in an Oxidation bath at 80 degree C. for 8 minutes, which contained 150 mL/L CUPOSITTM Z (Dow Electronics Materials) and100 mL/L of CIRCUPOSITTM MLB Promoter 213 (Dow Electronics Materials), and then rinsed with R.O. water for 3 minutes.
  • the drilled laminates were dipped in 50 mL/L of CIRCUPOSITTM MLB Neutralizer 216-5 bath (Dow Electronics Materials) at 40 degree C. for 5 minutes followed by water rinse for 3 minutes. The drilled laminates were then dried with an air knife for 2 minutes.
  • the dried glass cloth coupons as well as the de-smeared drilled laminates were treated in the same free radical initiator treatment as Example 1.
  • the test sample was dipped in a free radical initiator solution comprising 0.2 mol/L of AIBN in toluene at room temperature for 1 minute.
  • the sample was then dried in a fume hood at room temperature for 5 minutes.
  • both the glass cloth coupons and the drilled laminates were contacted with a solution comprising (A) and (B) above.
  • the solution comprising 0.026 mol/L of hexamethylene diamine and 0.013 mol/L of catechol was prepared using a K 2 HPO 4 /Citric Acid buffer solution. The pH of the solution was 4.5.
  • the samples were dipped in the aqueous solution described above at 80 degree C. for 2 to 4 hours. A water insoluble copolymer(A+B) film was formed on the surface of the samples.
  • Example 14 was processed in the same way as Example 13 except that step (2) was conducted in toluene without the presence of any free radical initiator.
  • Example 15 was a dopamine control example with free radical treatment. It was processed in the same way as for Example 13, except that step (3) was conducted using 0.013 mol/L dopamine aqueous solution buffered with 0.010 mol/L tris(hydroxymethyl)aminomethane and HCl to pH 8.5.
  • Example 16 was a dopamine control example without free radical treatment. It was processed in the same way as for Example 13 except that step (2) was conducted in toluene without the presence of any free radical initiator, and step (3) was conducted using 0.013 mol/L dopamine aqueous solution buffered with 0.010 mol/L tris(hydroxymethyl)aminomethane and HCl to pH 8.5.
  • Example 17 was a blank control for Example 13 to 16. It was processed in the same way as for Example 13 except that step (2) was conducted in toluene without the presence of any free radical initiator, and step (3) was conducted in distilled water alone, without any solute.
  • Example 15 and 16 indicated that poor copper coverage was observed on glass cloth coupons and in the through holes of drilled laminates that were treated by dopamine at 80 degree C. for 2 ⁇ 4 hours, whether with or without free radical treatment, although there was visible polydopamine film formed on the surface of treated sample.
  • the formation temperature of polydopamine affected its conditioner functionality. At room temperature for 24 hours, the polydopamine film formed showed good conditioner functionality. At 80 degree C. for 2 ⁇ 4 hours, the polydopamine film did not show conditioner functionality, although its appearance was similar to that formed at room temperature for 24 hours. A possible explanation to this phenomenon was that the priority of reactions may have changed with an increase of the treatment temperature.
  • Examples 18 to 25 were proceeded to examine the multiple functionalities of the copolymer(A+B) film formed by monomer pairs ((A)+(B)) treatment, including the conditioner functionality and the adhesion promoter functionality by Back Light Test and Peel Strength Test.
  • Drilled laminates S1141 the same as Example 13 were used as samples for back light test, and glass-fiber reinforced bare epoxy laminates S1141 (Size: 50 mm*150 mm*1 mm, Supplier: Shengyi Technology Co. Ltd., Glass transition temperature: 140 to 150 degree C., Abbreviated as bare laminates S1141) were used as test samples for peel strength between dielectric substrate and deposited metal film.
  • Bare laminates S1141 and drilled laminates S1141 were processed through the same de-smear process described in Example 13.
  • De-smeared bare laminates S1141 and de-smeared drilled laminates S1141 were processed through the same free radical initiator treatment process described in Example 13.
  • the sample was processed through the step of contacting with a solution comprising (A) and (B) above.
  • (A) is hexamethylene diamine and (B) is catechol.
  • the basic concentration was 0.013 mol/L.
  • the sample was treated at 80 degree C. for 2 to 4 hours. A water insoluble film was formed on the surface of treated samples.
  • the samples of bare laminates S1141 with the electroless copper film were processed through an electrolytic copper plating process.
  • the sample was first dipped in a acid cleaner bath at 40 degree C. for 5 minutes, which contained 50 mL/L RONACLEANTM LP 200 ACIDIC CLEANER (Dow Electronics Materials) and 50 mL/L 98% H 2 SO 4 (Sigma-Aldrich).
  • the sample was then rinsed with R.O. water for 3 minutes. After that, the sample was dipped in a 100 mL/L 98% H 2 SO 4 aqueous solution at 23 degree C. for 1 minute.
  • Electrolytic plating was then performed in an aqueous solution comprising 75 g/L copper ion from CuSO 4 , 100 mL/L 98% H 2 SO 4 (Sigma-Aldrich), 60 ppm chloride ion from 1 mol/L HCl (Sigma-Aldrich), 10 mL/L COPPER GLEAMTM 125T-AB Part B and 5 mL/L COPPER GLEAMTM 125T-AB Part A, at 20 ampere per square feet for 80 minutes.
  • the electrolytic plated sample was baked at 160 degree C. for 60 minutes before the peel strength test.
  • Example 21 was a blank control for Examples 18 to 20. It was processed in the same way as Example 18-20, except that step (2) was conducted in toluene without the presence of any free radical initiator, and step (3) was conducted in distilled water alone, without any solute.
  • Examples 22 to 24 were processed in the same way as Example 18-20 except that peel strength test was performed on another type of dielectric substrate, ABF-GX-13 film applied to a laminate substrate (Size: 100 mm*100 mm, Supplier: Ajinomoto fine-techno Co., Inc,), and that no back light tests were carried out.
  • Example 25 was a blank control for Examples 22 to 24. It was processed in the same way as Example 22-24, except that step (2) was conducted in toluene without the presence of any free radical initiator, and step (3) was conducted in distilled water alone, without any solute.

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KR20200065672A (ko) * 2018-11-30 2020-06-09 삼성전기주식회사 표면처리용 조성물 및 이를 이용한 표면처리방법
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